Revisiting the Solution Structure of Ceric Ammonium Nitrate

Demars, Thomas J.; Bera, Mrinal K.; Seifert, Soenke; Antonio, Mark R.; Ellis, Ross J.

doi:10.1002/anie.201502336

Title: Revisiting the Solution Structure of Ceric Ammonium Nitrate

Journal Article · Thu Apr 23 00:00:00 EDT 2015 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201502336· OSTI ID:1392400

Demars, Thomas J.; Bera, Mrinal K.; Seifert, Soenke; Antonio, Mark R.; Ellis, Ross J.

Ceric ammonium nitrate (CAN) is a single-electron-transfer reagent with unparalleled utility in organic synthesis, and has emerged as a vital feedstock in diverse chemical industries. Most applications use CAN in solution where it is assigned a monomeric [Ce-IV(NO3)(6)](2-) structure; an assumption traced to half-century old studies. Using synchrotron X-rays and Raman spectroscopy we challenge this tradition, converging instead on an oxo-bridged dinuclear complex, even in strong nitric acid. Thus, one equivalent of CAN is recast as a two-electron-transfer reagent and a redox-activated superbase, raising questions regarding the origins of its reactivity with organic molecules and giving new fundamental insight into the stability of polynuclear complexes of tetravalent ions.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science - Office of Basic Energy Sciences - Chemical Sciences, Geosciences, and Biosciences Division

DOE Contract Number:: AC02-06CH11357

OSTI ID:: 1392400

Journal Information:: Angewandte Chemie (International Edition), Vol. 54, Issue 26; ISSN 1433-7851

Publisher:: Wiley

Country of Publication:: United States

Language:: English

References (31)

Cerium oxide nanoparticle: a remarkably versatile rare earth nanomaterial for biological applications Xu, Can; Qu, Xiaogang NPG Asia Materials, Vol. 6, Issue 3 https://doi.org/10.1038/am.2013.88	journal	March 2014
Understanding the Formation and Evolution of Ceria Nanoparticles Under Hydrothermal Conditions Tyrsted, Christoffer; Ørnsbjerg Jensen, Kirsten Marie; Bøjesen, Espen Drath Angewandte Chemie, Vol. 124, Issue 36 https://doi.org/10.1002/ange.201204747	journal	August 2012
Electrolytic oxidation of Ce(III) in nitric acid and sulfuric acid media using a flow type cell Wei, Y.; Fang, B.; Arai, T. Journal of Applied Electrochemistry, Vol. 35, Issue 6 https://doi.org/10.1007/s10800-005-1820-7	journal	June 2005
Studies of the Ce(III)/Ce(IV) couple in multiphase systems containing a phase transfer reagent—I. Conditions for the extraction of Ce(IV) and electrode kinetics Pletcher, Derek; Valdes, Erika M. Electrochimica Acta, Vol. 33, Issue 4 https://doi.org/10.1016/0013-4686(88)80167-1	journal	April 1988
338. Extraction of ceric nitrate by solvents Wylie, A. W. Journal of the Chemical Society (Resumed) https://doi.org/10.1039/jr9510001474	journal	January 1951
Dinuclear complexes of tetravalent cerium in an aqueous perchloric acid solution Ikeda-Ohno, Atsushi; Tsushima, Satoru; Hennig, Christoph Dalton Transactions, Vol. 41, Issue 24 https://doi.org/10.1039/c2dt12406h	journal	January 2012
Ruthenium‐Catalyzed Selective and Efficient Oxygenation of Hydrocarbons with Water as an Oxygen Source Hirai, Yuichirou; Kojima, Takahiko; Mizutani, Yasuhisa Angewandte Chemie International Edition, Vol. 47, Issue 31 https://doi.org/10.1002/anie.200801170	journal	July 2008
Water as an Oxygen Source in the Generation of Mononuclear Nonheme Iron(IV) Oxo Complexes Lee, Yong-Min; Dhuri, Sunder N.; Sawant, Sarvesh C. Angewandte Chemie International Edition, Vol. 48, Issue 10 https://doi.org/10.1002/anie.200805670	journal	February 2009
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
Characterization of Aqueous Plutonium(IV) Nitrate Complexes by Extended X-ray Absorption Fine Structure Spectroscopy Allen, P. G.; Veirs, D. K.; Conradson, S. D. Inorganic Chemistry, Vol. 35, Issue 10 https://doi.org/10.1021/ic9511231	journal	January 1996
Coordination Structures and Supramolecular Architectures in a Cerium(III)–Malonamide Solvent Extraction System Ellis, Ross J.; Antonio, Mark R. Langmuir, Vol. 28, Issue 14 https://doi.org/10.1021/la3002916	journal	March 2012
Rare earth nanoparticles prevent retinal degeneration induced by intracellular peroxides Chen, Junping; Patil, Swanand; Seal, Sudipta Nature Nanotechnology, Vol. 1, Issue 2 https://doi.org/10.1038/nnano.2006.91	journal	October 2006
The Structure of Ammonium Hexanitratocerate(IV) in Solution ^1a Larsen, Russell D.; Brown, Glenn H. The Journal of Physical Chemistry, Vol. 68, Issue 10 https://doi.org/10.1021/j100792a502	journal	October 1964
EXAFS analysis of the L ₃ edge of Ce in CeO ₂ : effects of multi-electron excitations and final-state mixed valence Fonda, E.; Andreatta, D.; Colavita, P. E. Journal of Synchrotron Radiation, Vol. 6, Issue 1 https://doi.org/10.1107/S0909049598010280	journal	January 1999
Recent Advances in Synthetic Transformations Mediated by Cerium(IV) Ammonium Nitrate Nair, Vijay; Balagopal, Lakshmi; Rajan, Roshini Accounts of Chemical Research, Vol. 37, Issue 1 https://doi.org/10.1021/ar030002z	journal	January 2004
Crystal structure of ceric ammonium nitrate Beineke, Thomas A.; Delgaudio, J. Inorganic Chemistry, Vol. 7, Issue 4 https://doi.org/10.1021/ic50062a020	journal	April 1968
An Investigation of the Species Existing in Nitric Acid Solutions Containing Cerium(III) and Cerium(IV) ¹ Blaustein, Bernard D.; Gryder, John W. Journal of the American Chemical Society, Vol. 79, Issue 3 https://doi.org/10.1021/ja01560a012	journal	February 1957
Speciation and Structural Study of U(IV) and -(VI) in Perchloric and Nitric Acid Solutions Ikeda-Ohno, Atsushi; Hennig, Christoph; Tsushima, Satoru Inorganic Chemistry, Vol. 48, Issue 15 https://doi.org/10.1021/ic9004467	journal	August 2009
Understanding the Formation and Evolution of Ceria Nanoparticles Under Hydrothermal Conditions Tyrsted, Christoffer; Ørnsbjerg Jensen, Kirsten Marie; Bøjesen, Espen Drath Angewandte Chemie International Edition, Vol. 51, Issue 36 https://doi.org/10.1002/anie.201204747	journal	August 2012
Water as an Oxygen Source in the Generation of Mononuclear Nonheme Iron(IV) Oxo Complexes Lee, Yong-Min; Dhuri, Sunder N.; Sawant, Sarvesh C. Angewandte Chemie, Vol. 121, Issue 10 https://doi.org/10.1002/ange.200805670	journal	February 2009
Electrochemical and Complexation Behavior of Neptunium in Aqueous Perchlorate and Nitrate Solutions Ikeda-Ohno, Atsushi; Hennig, Christoph; Rossberg, André Inorganic Chemistry, Vol. 47, Issue 18 https://doi.org/10.1021/ic8009095	journal	September 2008
Ruthenium‐Catalyzed Selective and Efficient Oxygenation of Hydrocarbons with Water as an Oxygen Source Hirai, Yuichirou; Kojima, Takahiko; Mizutani, Yasuhisa Angewandte Chemie, Vol. 120, Issue 31 https://doi.org/10.1002/ange.200801170	journal	July 2008
Infrared and Raman spectra of the cerium(IV) ion – nitrate ion – water system Miller, J. T.; Irish, D. E. Canadian Journal of Chemistry, Vol. 45, Issue 2 https://doi.org/10.1139/v67-030	journal	January 1967
Crystal Structure and Solution Species of Ce(III) and Ce(IV) Formates: From Mononuclear to Hexanuclear Complexes Hennig, Christoph; Ikeda-Ohno, Atsushi; Kraus, Werner Inorganic Chemistry, Vol. 52, Issue 20 https://doi.org/10.1021/ic400999j	journal	September 2013
Cerium Valence in Cerium-Exchanged Preyssler's Heteropolyanion through X-ray Absorption Near-Edge Structure Antonio, Mark R.; Soderholm, L. Inorganic Chemistry, Vol. 33, Issue 26 https://doi.org/10.1021/ic00104a004	journal	December 1994
Application of lanthanide reagents in organic synthesis Molander, Gary A. Chemical Reviews, Vol. 92, Issue 1 https://doi.org/10.1021/cr00009a002	journal	January 1992
Influence of double-electron transitions on the EXAFS L edges of rare-earth systems Chaboy, Jesús; Marcelli, Augusto; Tyson, Trevor A. Physical Review B, Vol. 49, Issue 17 https://doi.org/10.1103/PhysRevB.49.11652	journal	May 1994
The Crystal Structure of Hydronium Cerium (III) Nitrate Hydrate, Ce(NO3)5(H3O)2 · H2O Guillou, N.; Auffredic, J. P.; Louër, M. Journal of Solid State Chemistry, Vol. 106, Issue 2 https://doi.org/10.1006/jssc.1993.1289	journal	October 1993
Cerium(IV) Ammonium NitrateA Versatile Single-Electron Oxidant Nair, Vijay; Deepthi, Ani Chemical Reviews, Vol. 107, Issue 5 https://doi.org/10.1021/cr068408n	journal	May 2007
Surface-Charge-Dependent Cell Localization and Cytotoxicity of Cerium Oxide Nanoparticles Asati, Atul; Santra, Santimukul; Kaittanis, Charalambos ACS Nano, Vol. 4, Issue 9 https://doi.org/10.1021/nn100816s	journal	August 2010
Cyclometalated Iridium(III) Aquo Complexes: Efficient and Tunable Catalysts for the Homogeneous Oxidation of Water McDaniel, Neal D.; Coughlin, Frederick J.; Tinker, Leonard L. Journal of the American Chemical Society, Vol. 130, Issue 1 https://doi.org/10.1021/ja074478f	journal	January 2008

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